Stable mass polymerizable polycycloolefin compositions as 3d printing materials and a method of fabrication thereof

ABSTRACT

Embodiments in accordance with the present invention encompass compositions encompassing a latent organo-ruthenium compound, a pyridine compound, a photosensitizer and an ultra violet light blocking compound along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said composition is exposed to suitable actinic radiation to form a substantially transparent film or a three dimensional object. Surprisingly, the compositions are very stable at ambient conditions to temperatures up to 80° C. for several days and undergo mass polymerization only when subjected to actinic radiation under inert atmosphere such as for example a blanket of nitrogen. Accordingly, compositions of this invention are useful in various opto-electronic applications, including as 3D printing materials, coatings, encapsulants, fillers, leveling agents, among others.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/958,832, filed Jan. 9, 2020, which is incorporated herein byreference in its entirety.

BACKGROUND OF THE INVENTION Field of the Invention

Embodiments in accordance with the present invention relate generally toa single component mass polymerizable polycycloolefin monomercompositions in combination with a latent organo-ruthenium compound, aphotosensitizer, a pyridine compound and a compound capable of blockingthe ultraviolet light. The compositions of this invention exhibit longstorage stability at temperatures ranging from ambient temperature to80° C. especially when stored in inert and dark atmosphere, and undergomass polymerization only when subjected to suitable actinic radiation toform transparent optical layers having utility in a variety ofopto-electronic applications including as 3D printing materials,encapsulants, coatings, and fillers. More specifically, this inventionrelates to single component stable compositions encompassing norbornene(NB) based olefinic monomers, which have high optical transparency andexhibit desirable properties for fabricating devices, such as opticalsensors, light emitting diodes (LEDs), organic light emitting diodes(OLED), 3D printing materials, among other devices.

Description of the Art

Organic light emitting diodes (OLEDs) are gaining importance in avariety of applications, including flat panel televisions and otherflexible displays, among other applications. However, conventionalOLEDs, particularly, bottom emitting OLEDs suffer from a drawback inthat only about half of the generated photons are emitted into the glasssubstrate out of which 25% are extracted into air. The other half of thephotons are wave-guided and dissipated in the OLED stack. This loss ofphotons is primarily attributed to the refractive index (n) mismatchbetween the organic layers (n=1.7-1.9) and the glass substrate (n=1.5).By matching the refractive index of the substrate (n=1.8) and organiclayers and augmenting the distance of the emission zone to the cathodeto suppress plasmonic losses light extraction into the substrate can beincreased to 80-90%. See, for example, G. Gaertner et al., Proc. OfSPIE, Vol. 6999, 69992T pp 1-12 (2008).

In addition, OLEDs also pose other challenges; in that OLEDs beingorganic materials, they are generally sensitive to moisture, oxygen,temperature, and other harsh conditions. Thus, it is imperative thatOLEDs are protected from such harsh atmospheric conditions. See forexample, U. S. Patent Application Publication No. US2012/0009393 A1.

In order to address some of the issues faced by the art, U.S. Pat. No.8,263,235 discloses use of a light emitting layer formed from at leastone organic light emitting material and an aliphatic compound not havingan aromatic ring, and a refractive index of the light emitting from 1.4to 1.6. The aliphatic compounds described therein are generally avariety of polyalkyl ethers, and the like, which are known to beunstable at high temperatures, see for example, Rodriguez et al., I & ECProduct Research and Development, Vol. 1, No. 3, 206-210 (1962).

U.S. Pat. No. 9,944,818 discloses a two component mass polymerizablecomposition which is capable of tailoring to the desirable refractiveindex and is suitable as a filler and a protective coating material,thus potentially useful in the fabrication of a variety of OLED devices.Although this approach may provide certain advantages it still suffersfrom the drawback of being two component system and in addition organicpolymers alone may not be able to provide required high refractive indexfor the OLED applications. Furthermore, there is also a need for masspolymerizable compositions which are stable at temperatures ranging fromroom temperatures up to 80° C. for several days such that thecompositions can be stored at various operating conditions such as forexample, vat 3D printing, where liquid compositions are stored in a 3Dprinter as well as OLED fabrication conditions, and yet the liquidcomposition polymerizes instantly when subjected to suitable photolyticconditions and/or higher temperatures. In addition, it has been observedthat especially under 3D printing conditions the compositions stored inthe vat may prematurely polymerize either due to air and/or exposure tolight.

Accordingly, there is still a need for filler materials that complementthe refractive index of OLEDs and yet exhibit high transparency and goodthermal properties, among other desirable properties. In addition, it isdesirable that such organic filler materials readily form a permanentprotective coatings and are available as a single component compositionfor dispensing with such OLED layers or in a vat 3D printing operations.

Thus, it is an object of this invention to provide compositions thatovercome the gaps faced by the art. More specifically, it is an objectof this invention to provide a single component composition that willmass polymerize under the conditions of the fabrications of 3D printingand/or fabrications of an OLED device. It is further an object of thisinvention to provide stable single component mass polymerizablecomposition with no change in viscosity at or below normal storageconditions, including up to a temperature of about 80° C. but whichundergoes mass polymerization only under the process conditions in whichthe 3D object or an OLED device is finally fabricated, such as forexample by the use of radiation.

Other objects and further scope of the applicability of the presentinvention will become apparent from the detailed description thatfollows.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that by employing a single componentcomposition, it is now possible to fabricate a 3D object or an OLEDdevice having a transparent optical layer which features hithertounachievable properties, i.e., refractive index in the range of 1.4 to1.8 or higher, high colorless optical transparency, desirable filmthickness of the filler layer typically in the range of 10 to 20 μm butcan be tailored to lower or higher film thickness depending upon theintended application, compatible with the OLED stack, particularly thecathode layer (a very thin layer on the top of the OLED stack),compatible with polymerization of the formulation on the OLED stack,including fast polymerization time and can be photolytically treated,adhesion to both OLED stack and glass cover, and the like. It is alsoimportant to note that the compositions of this invention are expectedto exhibit good uniform leveling across the OLED layer which typicallyrequires a low viscosity. Further, compositions of this invention arealso expected to exhibit low shrinkage due to their rigidpolycycloolefinic structure. In addition, as the components of thisinvention undergo fast mass polymerization upon application they do notleave behind any fugitive small molecules which can damage the OLEDstack. Generally, no other small molecule additives need to be employedthus offering additional advantages. Most importantly, the compositionsof this invention are stable (i. e., no change in viscosity) at ambientatmospheric conditions including up to 80° C. for several hours toseveral days, especially when kept under inert conditions, and undergomass polymerization only upon UV exposure. Most importantly, thecompositions of this invention exhibit excellent shelf life stability inthat the compositions of this invention retain their initial viscosityfor several days, at least five to ten days.

Advantageously, the compositions of this invention are also compatiblewith a “one drop fill” (commonly known as “ODF”). In a typical ODFprocess, which is commonly used to fabricate a top emission OLED device,a special optical fluid is applied to enhance the transmission of lightfrom the device to the top cover glass, and the fluid is dispensed by anODF method. Although the method is known as ODF which can be misleadingbecause several drops or lines of material are generally dispensedinside the seal lines. After applying the fluid, the fluid spreads outas the top glass is laminated, analogous to die-attach epoxy. Thisprocess is generally carried out under vacuum to prevent air entrapment.The present invention allows for a material of low viscosity whichreadily and uniformly coats the substrate with rapid flow in a shortperiod of time. Even more advantageously, the present inventionovercomes the deficiencies faced by the prior art in that a singlecomponent composition is much more convenient than employing a twocomponent system especially in an ODF method. Furthermore thecomposition of the invention when used in accordance with the processconditions as provided herein provides more transparent 3D objectshaving good mechanical and thermal properties.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments in accordance with the present invention are described belowwith reference to the following accompanying figures and/or images.Where drawings are provided, it will be drawings which are simplifiedportions of various embodiments of this invention and are provided forillustrative purposes only.

FIG. 1 shows a three dimensional vertical bar printed using a FlashforgeHunter DLP 3D printer using a composition embodiment and a processembodiment of this invention.

FIG. 2 shows several three dimensional vertical bars printed using aFlashforge Hunter DLP 3D printer using various composition embodimentsand a process embodiment of this invention.

FIG. 3 shows a three dimensional complex object printed using aFlashforge Hunter DLP 3D printer using a composition embodiment and aprocess embodiment of this invention.

FIG. 4 shows another three dimensional complex object printed using aFlashforge Hunter DLP 3D printer using a composition embodiment and aprocess embodiment of this invention.

FIGS. 5 to 7 show photographs of the fabricated objects formed fromvarious compositions of this invention.

FIG. 8 shows a three dimensional vertical bar printed using a FlashforgeHunter DLP 3D printer, which was printed under ambient atmosphereconditions without a nitrogen blanket.

DETAILED DESCRIPTION

The terms as used herein have the following meanings:

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the claimsappended hereto, are subject to the various uncertainties of measurementencountered in obtaining such values, unless otherwise indicated, allare to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous,inclusive of both the minimum and maximum values of the range as well asevery value between such minimum and maximum values. Still further,where a range refers to integers, every integer between the minimum andmaximum values of such range is included. In addition, where multipleranges are provided to describe a feature or characteristic, such rangescan be combined. That is to say that, unless otherwise indicated, allranges disclosed herein are to be understood to encompass any and allsub-ranges subsumed therein. For example, a stated range of from “1 to10” should be considered to include any and all sub-ranges between theminimum value of 1 and the maximum value of 10. Exemplary sub-ranges ofthe range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8,and 5.5 to 10, etc.

As used herein, “hydrocarbyl” refers to a group that contains carbon andhydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl,aralkyl, alkaryl, and alkenyl. The term “halohydrocarbyl” refers to ahydrocarbyl group where at least one hydrogen has been replaced by ahalogen. The term perhalocarbyl refers to a hydrocarbyl group where allhydrogens have been replaced by a halogen.

As used herein, the expression “alkyl” means a saturated, straight-chainor branched-chain hydrocarbon substituent having the specified number ofcarbon atoms. Particular alkyl groups are methyl, ethyl, n-propyl,isopropyl, n-butyl, iso-butyl, tert-butyl, and so on. Derivedexpressions such as “alkoxy”, “thioalkyl”, “alkoxyalkyl”,“hydroxyalkyl”, “alkylcarbonyl”, “alkoxycarbonylalkyl”,“alkoxycarbonyl”, “diphenylalkyl”, “phenylalkyl”, “phenylcarboxyalkyl”and “phenoxyalkyl” are to be construed accordingly.

As used herein, the expression “cycloalkyl” includes all of the knowncyclic groups. Representative examples of “cycloalkyl” includes withoutany limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, and the like. Derived expressions such as“cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl”are to be construed accordingly.

As used herein, the expression “perhaloalkyl” represents the alkyl, asdefined above, wherein all of the hydrogen atoms in said alkyl group arereplaced with halogen atoms selected from fluorine, chlorine, bromine oriodine. Illustrative examples include trifluoromethyl, trichloromethyl,tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl,pentabromoethyl, pentaiodoethyl, and straight-chained or branchedheptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl,nonachlorobutyl, undecafluoropentyl, undecachloropentyl,tridecafluorohexyl, tridecachorohexyl, and the like. Derived expression,“perhaloalkoxy”, is to be construed accordingly. It should further benoted that certain of the alkyl groups as described herein, such as forexample, “alkyl” may partially be fluorinated, that is, only portions ofthe hydrogen atoms in said alkyl group are replaced with fluorine atomsand shall be construed accordingly.

As used herein the expression “acyl” shall have the same meaning as“alkanoyl”, which can also be represented structurally as “R—CO—,” whereR is an “alkyl” as defined herein having the specified number of carbonatoms. Additionally, “alkylcarbonyl” shall mean same as “acyl” asdefined herein. Specifically, “(C₁-C₄)acyl” shall mean formyl, acetyl orethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as“acyloxy” and “acyloxyalkyl” are to be construed accordingly.

As used herein, the expression “aryl” means substituted or unsubstitutedphenyl or naphthyl. Specific examples of substituted phenyl or naphthylinclude o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl,2-methylnaphthyl, etc. “Substituted phenyl” or “substituted naphthyl”also include any of the possible substituents as further defined hereinor one known in the art.

As used herein, the expression “arylalkyl” means that the aryl asdefined herein is further attached to alkyl as defined herein.Representative examples include benzyl, phenylethyl, 2-phenylpropyl,1-naphthylmethyl, 2-naphthylmethyl and the like.

As used herein, the expression “alkenyl” means a non-cyclic, straight orbranched hydrocarbon chain having the specified number of carbon atomsand containing at least one carbon-carbon double bond, and includesethenyl and straight-chained or branched propenyl, butenyl, pentenyl,hexenyl, and the like. Derived expression, “arylalkenyl” and fivemembered or six membered “heteroarylalkenyl” is to be construedaccordingly. Illustrative examples of such derived expressions includefuran-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.

As used herein, the expression “heteroaryl” includes all of the knownheteroatom containing aromatic radicals. Representative 5-memberedheteroaryl radicals include furanyl, thienyl or thiophenyl, pyrrolyl,isopyrroyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl,and the like. Representative 6-membered heteroaryl radicals includepyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the likeradicals. Representative examples of bicyclic heteroaryl radicalsinclude, benzofuranyl, benzothiophenyl, indolyl, quinolinyl,isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl,pyridothienyl, and the like radicals.

“Halogen” or “halo” means chloro, fluoro, bromo, and iodo.

In a broad sense, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a few of the specificembodiments as disclosed herein, the term “substituted” meanssubstituted with one or more substituents independently selected fromthe group consisting of (C₁-C₆)alkyl, (C₂-C₆)alkenyl,(C₁-C₆)perfluoroalkyl, phenyl, hydroxy, —CO₂H, an ester, an amide,(C₁-C₆)alkoxy, (C₁-C₆)thioalkyl and (C₁-C₆)perfluoroalkoxy. However, anyof the other suitable substituents known to one skilled in the art canalso be used in these embodiments.

It should be noted that any atom with unsatisfied valences in the text,schemes, examples and tables herein is assumed to have the appropriatenumber of hydrogen atom(s) to satisfy such valences.

By the term “latent organo-transition metal catalyst” is meantorgano-transition metal compounds that show little or no catalyticactivity at a particular (usually ambient atmospheric conditions)temperature and initiate such activity either upon heat or light orboth. Generally the catalytic activity of the catalyst can be keptlatent for a prolonged periods of time, which can range from five daysor longer especially when it is stored at room temperature or lower in adark atmosphere. Higher temperatures and/or light may accelerate thecatalytic activity.

By the term “derived” is meant that the polymeric repeating units arepolymerized (formed) from, for example, polycyclic norbornene-typemonomers in accordance with formulae (I) or (IV) wherein the resultingpolymers are ring opened metathesis polymerized (ROMP), for example, the2,3 double bond of norbornene-type monomers are ring opened andpolymerized as shown below:

Accordingly, in accordance with the practice of this invention there isprovided a single component composition encompassing

a) one or more monomers of formula (I):

wherein:

m is an integer 0, 1 or 2;

R₁, R₂, R₃ and R₄ are the same or different and each independentlyselected from the group consisting of hydrogen, halogen, methyl, ethyl,linear or branched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl,hydroxy(C₁-C₁₆)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl,perfluoro(C₆-C₁₀)aryl, perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl,tri(C₁-C₆)alkoxysilyl and a group of formula (A):

—Z-Aryl  (A)

wherein:

Z is a bond or a group selected from the group consisting of:

(CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O, (CR₅R₆)_(a)—O—(CR₅R₆)_(b),(CR₅R₆)_(a)—O—(SiR₅R₆)_(b), (CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b),(CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b), (CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a andb are integers which may be the same or different and each independentlyis 1 to 12;

R₅ and R₆ are the same or different and each independently selected fromthe group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linear or branched(C₃-C₆)alkyloxy, acetoxy, (C₂-C₆)acyl, hydroxymethyl, hydroxyethyl,linear or branched hydroxy(C₃-C₆)alkyl, phenyl and phenoxy;

Aryl is phenyl or phenyl substituted with one or more of groups selectedfrom the group consisting of methyl, ethyl, linear or branched(C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linear or branched(C₃-C₆)alkyloxy, acetoxy, (C₂-C₆)acyl, hydroxymethyl, hydroxyethyl,linear or branched hydroxy(C₃-C₆)alkyl, phenyl and phenoxy;

b) an organo-ruthenium compound selected from the group consisting of acompound of formula (II) and a compound of formula (III):

wherein

L is P(R)₃, wherein each R is independently selected from the groupconsisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl,(C₃-C₈)cycloalkyl and (C₆-C₁₀)aryl;

R₇ and R₈ are the same or different and each independently selected fromthe group consisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl,methoxy, ethoxy and linear or branched (C₃-C₆)alkyloxy;

R₉ is selected from the group consisting of methyl, ethyl, linear orbranched (C₃-C₆)alkyl, (C₆-C₁₀)aryl and (C₆-C₁₀)aryl(C₁-C₆)alkyl;

Ar₁, Ar₂ and Ar₃ are the same or different and each independentlyselected from the group consisting of substituted or unsubstitutedphenyl, substituted or unsubstituted biphenyl and substituted orunsubstituted naphthyl, wherein each of said substituents areindependently selected from the group consisting of methyl, ethyl andlinear or branched (C₃-C₆)alkyl;

c) a compound of formula (IV) or a compound of formula (V):

wherein

n is an integer from 0 to 4;

each R₁₀ is independently selected from the group consisting ofhydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl andtert-butyl;

R₁₁ is selected from the group consisting of methyl, ethyl, linear orbranched (C₃-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linear or branched(C₃-C₆)alkoxy, (C₆-C₁₀)aryloxy and halogen;

d) a photoactive compound of formula (VI):

wherein

Y is halogen; and

R₃₀ and R₃₁ are the same or different and independently of each otherselected from the group consisting of hydrogen, methyl, ethyl, linear orbranched (C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)aryloxy;and

e) a compound of formula (VII):

wherein

n is an integer from 0 to 4;

each R₃₂ is independently selected from the group consisting ofhydrogen, methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)aryloxy;

said composition is in a clear liquid form at room temperature.

As used herein the Aryl may further include the following:

substituted or unsubstituted biphenyl of formula:

substituted or unsubstituted naphthyl of formula:

substituted or unsubstituted terphenyl of formula:

substituted or unsubstituted anthracenyl of formula:

substituted or unsubstituted fluorenyl of formula:

where R_(x) in each occurrence is independently selected from methyl,ethyl, linear or branched (C₃-C₁₂)alkyl or (C₆-C₁₀)aryl.

As noted, the monomer of formula (I) is having a refractive index of atleast 1.5. The composition is in a clear liquid form at roomtemperature. Surprisingly, as noted above, the compositions of thisinvention are stable at temperatures ranging from room temperature to80° C., thus offering excellent shelf life stability. As used herein,“stable” means the composition of this invention remains clear withoutincrease of any viscosity when kept at temperatures ranging from roomtemperature to 80° C., especially when kept in a dark atmosphere, suchas for example, in amber colored containers in the absence of any light.Accordingly, in some embodiments, the composition of this inventionexhibits no viscosity change when stored at temperatures below 80° C.for a period of more than four (4) days. Accordingly, in someembodiments, the composition of this invention exhibits less than five(5) percent viscosity increase when stored at temperatures below 80° C.for a period of more than four (4) days. In some other embodiments, thecomposition of this invention exhibits less than ten (10) percentviscosity change when stored at temperatures below 80° C. for a periodof four (4) days to ten (10) days.

The monomers employed in the composition of this invention arethemselves known in the literature or can be prepared by any of theknown methods in the art to make such or similar types of monomers.

In addition, the monomers as described herein readily undergo masspolymerization, i.e., in their neat form without use of any solventswhen polymerized under mass ring open metathesis polymerization (ROMP)conditions using certain transition metal catalysts, such as forexample, organo-ruthenium and organo-osmium compounds. See for example,R. H. Grubbs et al., Handbook of Metathesis, Ed.: Wiley-VCH, Weinheim,Germany, 2003, R. H. Grubbs et al., Acc. Chem. Res. 2001, 34, 18-29, R.H. Grubbs et al., Angew. Chem. Int. Ed., 2006, 45, 3760-3765. Also, seeU.S. Pat. No. 6,838,489, pertinent portions of which are incorporatedherein by reference. The term “mass polymerization” as used herein shallhave the generally accepted meaning in the art. That is, apolymerization reaction that is generally carried out substantially inthe absence of a solvent. In some cases, however, a small proportion ofsolvent is present in the reaction medium. For example, such smallamounts of solvent may be used to dissolve the latent catalyst and/orthe activator or convey the same to the reaction medium. Also, somesolvent may be used to reduce the viscosity of the monomer. The amountof solvent that can be used in the reaction medium may be in the rangeof 0 to 5 weight percent based on the total weight of the monomersemployed. Any of the suitable solvents that dissolves the catalyst,activator and/or monomers can be employed in this invention. Examples ofsuch solvents include alkanes, cycloalkane, toluene, THF,dichloromethane, dichloroethane, and the like.

Advantageously, it has now been found that one or more of the monomersthemselves can be used to dissolve the latent catalyst as well as theactivator and thus avoiding the need for the use of solvents. Inaddition, one monomer can itself serve as a solvent for the othermonomer and thus eliminating the need for an additional solvent. Forexample, if first monomer of formula (I) is a solid at room temperature,then the second monomer of formula (I), which is liquid at roomtemperature can be used as a solvent for the first monomer of formula(I) which is a solid or vice versa. Therefore, in such situations morethan one monomer can be employed in the composition of this invention.

Accordingly, it has now been surprisingly found that monomers of formula(I) serve as high refractive index materials imparting high refractiveindex to the resulting polymeric film upon mass polymerization at atemperature and/or condition different from the application of thecomposition onto a desirable substrate. In general, the monomers offormula (I) which are suitable in this invention feature a refractiveindex of at least 1.5. In some embodiments the refractive index of themonomers of formula (I) is higher than 1.5. In some other embodimentsthe refractive index of the monomers of formula (I) is in the range fromabout 1.5 to 1.6. In yet some other embodiments the refractive index ofthe monomers of formula (I) is higher than 1.55, higher than 1.6 orhigher than 1.65. In some other embodiments it may even be higher than1.7.

In general, the composition of this invention exhibits low viscosity,which can be below 100 centipoise or lower. In some embodiments, theviscosity of the composition of this invention is less than 80centipoise. In some other embodiments the viscosity of the compositionof this invention is in the range from about 10 to 100 centipoise. Inyet some other embodiments the viscosity of the composition of thisinvention is lower than 70 cP, lower than 60 cP, lower than 40 cP, lowerthan 20 cP. In some other embodiments it may even be lower than 10 cPand may vary from as low as 4 cP to 9 cP.

When the composition of this invention contains two or more monomers,for example, they can be present in any desirable amounts that wouldbring about intended benefit, including either refractive indexmodification or viscosity modification or both. Accordingly, the molarratio of first monomer of formula (I) to second monomer of formula (II)can be from 1:99 to 99:1. In some embodiments, the molar ratio of firstmonomer of formula (I):second monomer of formula (I) is in the rangefrom 5:95 to 95:5; in some other embodiments it is from 10:90 to 90:10;it is from 20:80 to 80:20; it is from 30:70 to 70:30; it is from 60:40to 40:60; and it is 50:50, and so on. Similarly, when more than twodifferent monomers of formula (I) are employed, any ratios of suchmonomers can be used that would bring about the intended result.

In general, the compositions in accordance with the present inventionencompass the above described one or more of the monomer of formula (I)and if needed additional monomers of formula (I) distinct from eachother, as it will be seen below, various composition embodiments areselected to provide properties to such embodiments that are appropriateand desirable for the use for which such embodiments are directed, thussuch embodiments are tailorable to a variety of specific applications.

For example, as already discussed above, proper combination ofdistinctive monomers of formula (I) makes it possible to tailor acomposition having the desirable refractive index, viscosity and opticaltransmission properties. In addition, as described further herein it maybe desirable to include other polymeric or monomeric materials, such asfor example inorganic nanoparticles which are compatible to providedesirable optical properties depending upon the end use application.Accordingly, the compositions of this invention can also include otherhigh refractive polymeric materials and/or nanoparticles which willbring about such intended benefit. Examples of such polymers includewithout any limitation, poly(α-methylstyrene), poly(vinyl-toluene),copolymers of α-methylstyrene and vinyl-toluene, and the like. Examplesof nanoparticles are described further in detail below.

Advantageously, it has further been found that the compositions of thisinvention can also contain additional monomers. In some embodiments, thecomposition according to this invention may further contain one or moremonomers selected from monomer of formula (VIII).

The monomer of formula (VIII) is:

wherein:

o is an integer from 0 to 2, inclusive;

D is SiR₂₁R₂₂R₂₃ or a group selected from:

—(CH₂)_(c)—O—SiR₂₁R₂₂R₂₃  (E);

—(CH₂)_(c)—SiR₂₁R₂₂R₂₃  (F); and

—(SiR₂₁R₂₂)_(c)—O—SiR₂₁R₂₂R₂₃  (G); wherein

c is an integer from 1 to 10, inclusive, and where one or more of CH₂ isoptionally substituted with (C₁-C₁₀)alkyl, (C₁-C₁₀)perfluoroalkyl or(C₆-C₁₄)aryl;

R₁₈, R₁₉ and R₂₀ are the same or different and independently of eachother selected from hydrogen, halogen and hydrocarbyl, where hydrocarbylis selected from methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl or (C₆-C₁₀)aryloxy; and

R₂₁, R₂₂ and R₂₃ are each independently of one another methyl, ethyl,linear or branched (C₃-C₉)alkyl, substituted or unsubstituted(C₆-C₁₄)aryl, methoxy, ethoxy, linear or branched (C₃-C₉)alkoxy orsubstituted or unsubstituted (C₆-C₁₄)aryloxy.

In this aspect of the invention, it has now been found that monomers offormula (VIII) provides further advantages. Namely, the monomers offormula (VIII) depending upon the nature of the monomer may impart highor low refractive index to the composition, thus it can be tailored tomeet the need. In addition, the monomers of formula (VIII) generallyimprove the adhesion properties and thus can be used as “adhesionmodifiers.” Finally, the monomers of formula (VIII) may exhibit lowviscosity and good solubility for the latent catalyst and/or activator,among various other advantages.

In some embodiments, the composition of this invention contains firstand second monomer of formula (I) distinct from each other and one ofsaid first and second monomers having a refractive index of at least 1.5and viscosity below 100 centipoise, and wherein said first monomer iscompletely miscible with said second monomer to form a clear solution.However, as noted, any one or more of monomers of formula (VIII) canalso be used in this embodiment of the invention.

In some embodiments the composition of this invention may also containone or more monomers of formula (IX):

wherein

R₁₆ and R₁₇ are the same or different and each independently selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₆)alkyl, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,acetoxy, (C₂-C₆)acyl, phenyl and phenoxy; or

R₁₆ taken together with R₁₇ and the carbon atoms to which they areattached to form a (C₅-C₇)carbocyclic ring optionally containing one ormore double bonds;

R₁₈ is hydrogen, halogen, methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, hydroxy, methoxy,ethoxy, linear or branched (C₃-C₁₆)alkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, —O(CO)R₁₉ and —O(CO)OR₁₉, where R₁₉ ismethyl, ethyl, linear or branched (C₃-C₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl.

Accordingly, any of the monomers within the scope of monomer of formula(I) or formula (VIII) can be employed in the composition of theinvention. Representative examples of monomer of formula (I) or formula(VIII) include the following without any limitations:

Representative examples of monomer of formula (IX) include the followingwithout any limitations:

Surprisingly, it has been further found that utilization of additionaladditives which are capable of scavenging any of halide radicals formedduring photo exposure provides additional benefits in forming clearobjects from the compositions of this invention. In addition, suchadditives may also act as chain terminators to prevent dark reaction.The dark reaction as used herein is meant by polymer chain growth in theunexposed areas. Any of additives which may be helpful in scavengingsuch halide radicals and chain termination can be employed in thisinvention. It has now been particularly found that use of certainacrylates provide advantageous benefits as noted herein among otherbenefits. Exemplary acrylates that may be suitable include without anylimitation alkyl acrylates, aryl acrylates, alkyl methacrylates, arylmethacrylates, and the like. Non-limiting examples of such specificacrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate,isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butylacrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate,n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate,iso-butyl methacrylate, tert-butyl methacrylate, phenyl methacrylate,and the like.

Any of the amount of acrylate monomer that will bring about the intendedbenefit can be used in the composition of this invention. Generally,such amounts depend upon various other additives used in the compositionof this invention as is readily appreciated by one of skill in the art.In some embodiments one or more of acrylate monomers are employed insufficient quantities, which can range from about 1 molar part to 50molar parts when compared with 5,000 to 10,000 molar parts of monomersof formula (I) or in combination with monomers of formulae (VIII) and/or(IX). In some embodiments, the amount of acrylate monomer used is about5 to 20 molar parts when compared with 10,000 molar parts of combinedmonomers of formulae (I), (VIII) and (IX), if employed.

As noted, the composition of this invention contains at least one oforgano-ruthenium compound of formulae (II) or (III) that would bringabout the mass polymerization as described herein under ROMP conditionswhen the composition is subjected suitable actinic radiation. Generally,such organo-ruthenium compounds of formulae (II) or (III) are “latent”and become active only under certain conditions. Again, as used hereinthe term “latent” means that the organo-ruthenium catalysts used in thecomposition of this invention remain inactive for a prolonged period oftime when the composition of this invention is stored at ambientconditions to temperatures up to 80° C. Accordingly, in some embodimentsthe organo-ruthenium catalysts remain latent for a period of more thanfour (4) days when stored at temperatures below 80° C. In some otherembodiments, the organo-ruthenium catalysts remain latent for a periodof four (4) days to ten (10) days when stored at temperatures below 50°C.

Generally, any of the latent organo-ruthenium compounds of formulae (II)or (III) that would bring about ring open metathesis polymerization ofthe monomers of formulae (I) or (VIII) or (IX) can be employed in thecomposition of this invention. More specifically, organo-rutheniumcompounds that show little or no activity at ambient temperatures can beemployed. That is, the latent catalysts that are stable at or near roomtemperature are more suitable in the composition of this invention. Asnoted, the latent catalysts may be activated by a variety of conditions,including without any limitation thermal, acid, light and chemicalactivation. The chemical activation may include use of thermal acidgenerator or photo acid generators.

Several of the latent catalysts that are suitable to be employed in thecompositions of this invention are known in the literature or can bereadily made by any of the known procedures in the art. See for example,Grubbs, et al., Organometallics, 2011, 30 (24): 6713-6717; Sutar et al.,Angew. Chem. Int. Ed. 2016, 55, 764-767; Leitgeh, et al., Monatsh Chem(2014) 145:1513-1517; van Hensbergen, et al., J. Mater. Chem. C. 2015,3, 693-702; Grubbs, et al., J. Am. Chem. Soc., 2009, 131, 203802039;Zak, et al., Eur. J. Inorg. Chem., 2014, 1131-1136; Gawin, et al., ACSCatal. 2017, 7, 5443-5449. Further examples of such catalysts can alsobe found in U.S. Pat. No. 9,328,132, pertinent portions of which areincorporated herein by reference.

Accordingly, in some embodiments, the composition of this inventioncontains an organo-ruthenium compound of formulae (II) or (III),wherein:

L is selected from the group consisting of P(iPr)₃, P(tert-Bu)₃, PCy₃and PPh₃;

R₇ and R₈ are the same or different and each independently selected fromthe group consisting of hydrogen, methyl, ethyl and isopropyl;

R₉ is selected from the group consisting of hydrogen, methyl, ethyl andisopropyl;

Ar₁, Ar₂ and Ar₃ are the same or different and each independentlyselected from the group consisting of phenyl, 2,6-dimethylphenyl,2,6-diethylphenyl, 2,6-di(isopropyl)phenyl and 2,4,6-trimethylphenyl.

Accordingly, a few of the exemplary latent catalysts, which are withinthe scope of organo-ruthenium compounds of formula (II) ororgano-ruthenium compounds of formula (III), without any limitationmaybe selected from the group consisting of:

As noted, the composition of this invention also contains a compound offormula (IV) or a compound of formula (V). Any of the compounds withinthe scope of compounds of formula (IV) or (V) can be used in thecomposition of this invention. In some embodiments the composition ofthis invention contains a compound of formula (IV) or a compound offormula (V), wherein:

n is an integer from 0 to 2;

each R₁₀ is independently selected from the group consisting of methyl,ethyl, iso-propyl and tert-butyl; and

R₁₁ is selected from the group consisting of methyl, ethyl, iso-propyl,tert-butyl, phenyl, methoxy, ethoxy, phenoxy, fluorine and chlorine.

Non-limiting examples of a compound of formula (IV) or a compound offormula (V) are selected from the group consisting of:

-   N,N-dimethylpyridin-4-amine (DMAP);-   N,N-diethylpyridin-4-amine;-   N,N-diisopropylpyridin-4-amine;-   N,N-di-tert-butylpyridin-4-amine;-   N,N-dimethyl-2-methylpyridin-4-amine;-   N,N-di-tert-butyl-2-methylpyridin-4-amine;-   2-methoxy-N,N-dimethylpyridin-4-amine;-   2-fluoro-N,N-dimethylpyridin-4-amine;-   N,N-dimethylquinolin-4-amine;-   N,N,2-trimethylquinolin-4-amine;-   2-methoxy-N,N-dimethylquinolin-4-amine; and-   2-chloro-N,N-dimethylquinolin-4-amine.

As noted, the composition of this invention further contains a compoundcapable of activating the organo-ruthenium compounds of formulae (II) or(III) when subjected to suitable photolytic conditions. Surprisingly ithas now been found that certain of the known photoactive compounds, suchas for example, a class of substituted xanthone derivatives can be usedfor this purpose, which are as illustrated by structural formula (VI).

Representative examples of the compounds of formula (VI), without anylimitation, may be listed as follows:

As noted, the composition of this invention further includes a compoundof formula (VII). Advantageously it has now been found thatincorporation of a compound of formula (VII) imparts surprisinglyfurther stability to the composition of this invention especially whenused in the surroundings of UV exposure, such as for example in a vat ofthe 3D printer. By inclusion of a compound of formula (VII) surprisinglyimproves the stability of the composition and the optical performance ofthe 3D articles made therefrom. It is believed that the compounds offormula (VII) function as UV blockers, among other functions, therebyimparting greater stability to the composition while in peripheralcontact with any UV light during the UV exposure of the compositionwhich is drawn out of the vat for forming the intended 3D objects.Therefore, any of the compounds which may function similarly to that ofcompounds of formula (VII) can also be employed in the composition ofthis invention, such as for example, any of the other known UV blockers.Any of the amounts of a compound of formula (VII) that would bring aboutthe desired benefit can be employed in the composition of thisinvention. Generally, such amounts may vary from about 1:200 molar partsof a compound of formula (VII):a compound of formula (II) or (III). Insome other embodiments such amounts are from about 1:100 molar parts ofa compound of formula (VII):a compound of formula (II) or (I); or 1:50molar parts of a compound of formula (VII):a compound of formula (I) or(III), and so on.

Representative examples of the compounds of formula (VII), without anylimitation, may be listed as follows:

Various other UV light blocking compounds and/or UV light absorbers thatcan be used in the composition of this invention include the following:

Wherein n and R₃₂ are as defined herein.

Representative compounds within the scope of compounds of formulae(VIIa) and (VIIb) may be represented as follows:

1,2-bis(4-(benzo[d]oxazol-2-yl)phenyl)ethene, available commercially asBenetex OB-1 from Mayzo; and

sodium2,2′-([1,1′-biphenyl]-4,4′-diylbis(ethene-2,1-diyl))dibenzenesulfonate,available commercially as Benetex OB-M1 from Mayzo.

As noted, surprisingly, it has now been found that employing a suitablecombination of a compound of formula (II) or a compound of formula (III)in combination with a compound of formula (IV) or a compound of formula(V) can trigger the mass polymerization of the monomers when thecomposition is subjected to either a suitable radiation, generally atwavelengths of from about 240 nm to 410 nm, the composition undergoesmass ring open-metathesis polymerization (ROMP) to form a transparentfilm or an object.

Any amount of organo-ruthenium compound of formulae (II) or (III) can beemployed in the composition of this invention which will bring about theintended result. Generally, the molar ratio of monomer:compound offormulae (II) or (III) is in the range of 10,000:1 to 5,000:1 or lower.In some other embodiments such molar ratio of monomer:compound offormula (II) is 15,000:1, 20,000:1 or higher.

Any amount of a compound of formula (IV) or a compound of formula (V)can be employed in the composition of this invention which will bringabout the intended result. Generally, the molar ratio of compound offormula (II) or (III):compound of formula (IV) or (V) is in the range of1:50 or higher. In some other embodiments such molar ratio of compoundof formula (II) or formula (III):compound of formula (IV) or (V) is1:10, 1:15, 1:20, 1:25, 1:30, 1:40, and so on.

In some embodiments the composition of this invention undergoes masspolymerization when exposed to suitable UV irradiation to form asubstantially transparent film. The monomers undergo mass polymerizationto form films which are substantially transparent to visible light. Thatis, most of the visible light is transmitted through the film. In someembodiments such film formed from the composition of this inventionexhibits a transmission of equal to or higher than 90 percent of thevisible light. In some other embodiments such film formed from thecomposition of this invention exhibits a transmission of equal to orhigher than 95 percent of the visible light.

In yet other embodiments the composition of this invention undergoesmass polymerization when exposed to suitable UV irradiation at atemperature from 80° C. to 100° C. to form a substantially transparentfilm or an object.

In some embodiments the compounds of formula (VI) can be activated atcertain wavelength of the electromagnetic radiation which can generallyrange from about 240 nm to 400 nm. Accordingly, any of the compoundswhich are active in this electromagnetic radiation can be employed inthe compositions of this invention which are stable to the 3Dfabrication methods. In some embodiments the wavelength of the radiationto activate the compounds of formula (VI) is 260 nm. In some otherembodiments the wavelength of the radiation to activate the compounds offormula (VI) is 310 nm. In yet some other embodiments the wavelength ofthe radiation to activate the compounds of formula (VI) is 395 nm.

However, any of the other known photoactive compounds which can activatethe latent organo-ruthenium compounds of formulae (II) or (III) employedherein can also be used in the composition of this invention. All suchcompounds are part of this invention.

In some embodiments of this invention the composition of this inventionmay additionally contain other photosensitizer compounds which canactivate the organo-ruthenium compounds of formulae (II) or (III) inorder to facilitate the mass polymerization of the monomers of formula(I) and monomers of formulae (VIII) or (IX), if present. For thispurpose, any suitable sensitizer compound can be employed in thecompositions of the present invention. Such suitable sensitizercompounds include, photosensitizers, such as, anthracenes,phenanthrenes, chrysenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes,xanthones, indanthrenes, and mixtures thereof. In some exemplaryembodiments, suitable sensitizer components include mixtures thereof.Generally, the photosensitizers absorb energy from the radiated lightsource and transfers that energy to the desirable substrate/reactantemployed in the composition of this invention.

The compositions in accordance with the present invention may furthercontain optional additives as may be useful for the purpose of improvingproperties of both the composition and the resulting object madetherefrom. Such optional additives for example may include anti-oxidantsand synergists. Any of the anti-oxidants that would bring about theintended benefit can be used in the compositions of this invention.Non-limiting examples of such antioxidants include pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (IRGANOX™ 1010from BASF), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl esterbenzenepropanoic acid (IRGANOX™ 1076 from BASF) and thiodiethylenebis[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)propionate] (IRGANOX™ 1035from BASF). Non-limiting examples of such synergists include certain ofthe secondary antioxidants which may provide additional benefits such asfor example prevention of autoxidation and thereby degradation of thecomposition of this invention and extending the performance of primaryantioxidants, among other benefits. Examples of such synergists include,tris(2,4-ditert-butylphenyl)phosphite, commercially available as IRGAFOS168 from BASF, among others.

In another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1).

In yet another embodiment of this invention, the composition of thisinvention encompasses a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene(PENB), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1).

In yet another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1).

In yet another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-dimethylphenyl-imino)methyl)phenoxy)ruthenium(Ru-2).

In yet another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diethylphenyl-imino)methyl)phenoxy)ruthenium(Ru-3).

In yet another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-4).

In yet another embodiment of this invention, the composition of thisinvention encompasses a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-3-phenyl-1H-inden-1-ylidene)-2-(methylthio)phenoxy-ruthenium-triphenylphosphinechloride (Ru-5).

In a further aspect of this invention there is provided a kit forforming a substantially transparent film. There is dispensed in this kita composition of this invention. Accordingly, in some embodiments thereis provided a kit in which there is dispensed one or more monomers offormula (I), an organo-ruthenium compound of formula (II) or anorgano-ruthenium compound of formula (III), a compound of formula (IV)or (V), a compound of formula (VI) and a compound of formula (VII), andoptionally one or more monomers of formula (VIII) or one or moremonomers of formula (IX) and various other additives as describedherein.

Accordingly, in some embodiments of this invention the kit according tothis invention contains one or more monomers of formula (I), anorgano-ruthenium compound of formula (II), a compound of formula (IV), acompound of formula (VI) and a compound of formula (VII).

In yet some other embodiments the kit according to this inventioncontains one or more monomers of formula (I), an organo-rutheniumcompound of formula (II), a compound of formula (IV), a compound offormula (VI), a compound of formula (VII) and one or more additives asdescribed herein.

In some embodiments, the aforementioned kit encompasses two or moremonomers of formula (I) distinct from one another as describedhereinabove. In some other embodiments the kit of this inventionencompasses at least two monomers wherein first monomer facilitatesdissolution of the second monomer and/or the organo-ruthenium compoundsof formulae (II) or (III) and the additives as described hereinabove.Any of the monomers of formula (I) as described herein can be used inthis embodiment. The molar ratio of first and the second monomer offormula (I) contained in these components can vary and may range from1:99 to 99:1, or 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 60:40to 40:60 or 50:50, and so on. In some other embodiments the kit mayencompass a composition wherein dispensed more than two monomers offormula (I), each distinct from one another. Further, as noted the firstmonomer of formula (I) is completely soluble in the second monomer offormula (I) to form a clear solution at room temperature. In someembodiments the monomer mixture may become a clear solution at slightlyelevated temperature, such as for example, 30° C. or 40° C. or 50° C.

In another aspect of this embodiment of this invention the compositionof this invention undergoes mass polymerization when subjected tosuitable radiation for a sufficient length of time to form a polymericfilm or a solid object. That is to say that the composition of thisinvention is poured onto a surface or onto a substrate which needs to beencapsulated, and exposed to suitable radiation in order for themonomers to undergo polymerization to form a solid transparent polymerwhich could be in the form of a transparent film or a solid object.Generally, as already noted above, such polymerization can take placewhen exposed to actinic radiation at wavelengths ranging from about 240nm to 410 nm. The compositions can also be subjected simultaneously tosuitable radiation and heat to cause mass polymerization. By practice ofthis invention it is now possible to obtain polymeric films on suchsubstrates which are substantially transparent film or solid objectsdepending on the method of fabrication employed. The “substantiallytransparent film” as used herein means that the films formed from thecomposition of this invention are optically clear in the visible light.Accordingly, in some embodiments of this invention such films are havingat least 90 percent of visible light transmission, in some otherembodiments the films formed from the composition of this inventionexhibit at least 95 percent of visible light transmission.

In some embodiments, the kit as described herein encompasses acomposition, which contains a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1).

In yet another embodiment of this invention, the kit as described hereinencompasses a composition of this invention containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1).

In yet another embodiment of this invention, the kit as described hereinencompasses a composition of this invention containing a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1).

In yet another embodiment of this invention, the kit as described hereinencompasses a composition of this invention containing a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-dimethylphenyl-imino)methyl)phenoxy)ruthenium(Ru-2).

In yet another embodiment of this invention, the kit as described hereinencompasses a composition of this invention containing a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diethylphenyl-imino)methyl)phenoxy)ruthenium(Ru-3).

In yet another embodiment of this invention, the kit as described hereinencompasses a composition of this invention containing a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-4).

In yet another embodiment of this invention, the kit as described hereinencompasses a composition of this invention containing a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-3-phenyl-1H-inden-1-ylidene)-2-(methylthio)phenoxy-ruthenium-triphenylphosphinechloride (Ru-5).

In yet another aspect of this invention there is further provided amethod of forming a substantially transparent film for the fabricationof a variety of optoelectronic device comprising:

forming a homogeneous clear composition comprising one or more monomersof formula (I), an organo-ruthenium compound of formula (II) or anorgano-ruthenium compound of formula (III), a compound of formula (IV)or (V), a compound of formula (VI), a compound of formula (VII), andoptionally one or more monomers of formula (VIII) or (IX) and one ormore additives as described herein.

coating a suitable substrate with the composition or pouring thecomposition onto a suitable substrate to form a film; and

either exposing the film to suitable radiation or heating the film to asuitable temperature to cause polymerization of the monomers.

The coating of the desired substrate to form a film with the compositionof this invention can be performed by any of the coating procedures asdescribed herein and/or known to one skilled in the art, such as by spincoating. Other suitable coating methods include without any limitationspraying, doctor blading, meniscus coating, ink jet coating and slotcoating. The mixture can also be poured onto a substrate to form a film.Suitable substrate includes any appropriate substrate as is, or may beused for electrical, electronic or optoelectronic devices, for example,a semiconductor substrate, a ceramic substrate, a glass substrate.

Next, the coated substrate is exposed to suitable actinic radiation,i.e., exposed to radiation of wavelength ranging from 240 nm to 410 nmas described herein to facilitate the mass polymerization. In someembodiments the substrate is exposed to radiation and baked at atemperature of from about 60° C. to about 90° C. for 2 minutes to 10minutes. In some other embodiments the substrate is exposed to radiationand baked at a temperature of from about 60° C. to about 90° C. for 5minutes to 20 minutes.

The films thus formed are then evaluated for their optical propertiesusing any of the methods known in the art. For example, the refractiveindex of the film across the visible spectrum can be measured byellipsometry. The optical quality of the film can be determined byvisual observation. Quantitatively the percent transparency can bemeasured by visible spectroscopy. Generally, the films formed accordingto this invention exhibit excellent optical transparent properties andcan be tailored to desirable refractive index as described herein.

Accordingly, in some of the embodiments of this invention there is alsoprovided a optically transparent film obtained by the masspolymerization of the composition as described herein. In anotherembodiment there is also provided an optoelectronic device comprisingthe transparent film of this invention as described herein.

As noted, the compositions of this invention can be used in any of theknown three dimensional (3D) printing technologies and other printingtechnologies. A few of the 3D printing procedures known in the artinclude continuous liquid interface production (CLIP), layer by layerapproach (LBL), inkjet printing and frontal polymerization method, suchas frontal ring open metathesis (FROMP) technique, see for exampleRobertson et al., Nature, Vol. 557, 223-227 (2018).

In a CLIP approach, a 3D object is continuously formed by projecting acontinuous sequence of UV images (generated by a digitallight-processing (DLP) imaging unit or a laser to generate the part)through an oxygen permeable, UV-transparent window below a liquid resinbath containing the compositions of this invention. The dead zonecreated above the window maintains a liquid interface below theadvancing part. Above the dead zone, the curing part is continuouslydrawn out of the resin bath. The suction forces resulted due to thisdrawing replenishes the resin bath at the same time. In this way variousparts of different dimensions up to several centimeters with partresolution lower than 100 microns can be fabricated.

In a 3D inkjet printing technology, the compositions of this inventioncan be used as photopolymerizable ink compositions to form lines andvias on a substrate, typically on a silicon wafer. A wide variety ofparts having utility in electronic and optoelectronic applications canthus be manufactured using the compositions of this invention. Nonlimiting examples of such applications include manufacturing of OLEDdevices on a variety of substrates, which can be produced substantiallyin a particle free environment at high yields. The compositions of thisinvention may act as organic encapsulant layers and/or as fillermaterials in some of such OLED devices.

Accordingly, in yet another aspect of this invention there is furtherprovided a method of forming a three dimensional object comprising:

providing a homogeneous clear composition in a suitable containerblanketed with an inert atmosphere, the composition comprising one ormore monomers of formula (I), at least one organo-ruthenium compound offormulae (II) or (III), a compound of formula (IV) or a compound offormula (V), a compound of formula (VI), a compound of formula (VII),and optionally one or more monomers of formula (VIII) and/or one or moremonomers of formula (IX) in combination with one or more additives asdescribed herein;

exposing to suitable UV radiation while drawing the composition from thecontainer; and

forming a three dimensional object.

Surprisingly, it has now been found that providing the composition in asuitable container blanketed with an inert atmosphere it is now possibleto form 3D objects which are free of any voids and exhibiting excellentoptical, thermal and mechanical properties. Such inert blanketedatmospheres can be achieved by using any of the inert gases which willbring about this effect. Non-limiting examples of such inert gasesinclude nitrogen, helium, argon, and the like. In some embodiments theinert atmosphere used is by way purging with dry nitrogen.

Accordingly, the 3D objects formed in accordance with the method of thisinvention exhibit excellent optical, thermal and mechanical properties.In general, the properties of these objects can be tailored to intendedend use. For example, the thermal properties of the 3D objects can betailored to be stable up to 180° C. or higher depending upon the typesof monomers of formula (I) in combination with monomers of formulae(VIII) or (IX), if employed, to form such 3D objects. Similarly, themechanical properties can also be tailored to desired mechanicalproperties simply by the selection of suitable monomers as describedherein. In general, by tailoring the proper choice of monomers the partspossessing very high impact strength can be fabricated. Most importantlythe compositions of this invention are stable to 3D printing conditionsand withstand the temperatures of up to 80° C. without any degradationand/or premature polymerization for several days ranging from about 5 toten days, thus offering long shelf life stability, among other benefits.In some embodiments the composition of this invention is stable at 80°C. for at least 6 days. In some other embodiments the composition ofthis invention is stable at 50° C. for at least 10 days. In yet someother embodiments the composition of this invention is stable at 80° C.for at least 8 days.

Accordingly, in some of the embodiments of this invention there is alsoprovided a three dimensional object comprising the composition of thisinvention which exhibits excellent optical, thermal and mechanicalproperties.

The following examples are detailed descriptions of methods ofpreparation and use of certain compounds/monomers, polymers andcompositions of the present invention. The detailed preparations fallwithin the scope of, and serve to exemplify, the more generallydescribed methods of preparation set forth above. The examples arepresented for illustrative purposes only, and are not intended as arestriction on the scope of the invention. As used in the examples andthroughout the specification the ratio of monomer to catalyst is basedon a mole to mole basis.

EXAMPLES

The following abbreviations have been used hereinbefore and hereafter indescribing some of the compounds, instruments and/or methods employed toillustrate certain of the embodiments of this invention:HexylTD—2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;CPD3—3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene;Ru-1—1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium;CPTX—1-chloro-4-propoxy-9H-thioxanthen-9-one;DMAP—N,N-dimethylpyridin-4-amine;BTBBT—(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene; Irganox1076—3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl esterbenzenepropanoic acid; Irgafos168—tris(2,4-ditert-butylphenyl)phosphite; phr—parts per hundred partsof monomer; TGA—thermogravimetric analysis.

Various monomers as used herein are either commercially available or canbe readily prepared following the procedures as described in theco-pending U.S. Pat. No. 9,944,818.

The following Examples demonstrate that the compositions of thisinvention are quite stable at 50° C. or at 80° C. for several days andcan very readily be mass polymerized by subjecting to UV light andthereby forming 3D objects as specified below.

Example 1 Printing of 3D Objects Under Nitrogen Blanket

In a glass brown bottle, CPTX (0.5 phr), Irganox 1076 (1 phr), Irgafos168 (0.25 phr), DMAP (0.1 molar part) and BTBBT (0.01 molar part) weredissolved in HexylTD (10,000 molar parts) via sonication at 40° C. for 1hour to form a clear solution. The solution was purged with nitrogen for8 hours. Ru-1 catalyst (1 molar part) was added in a glove box to thepurged solution and sonicated for 30 minutes to completely dissolve thecatalyst. Flashforge Hunter DLP 3D printer was used to print various 3Dparts, which was modified such that the space above the composition keptin the vat was blanketed with nitrogen.

FIG. 1 shows a photograph of a clear vertical bar, which can be printedcontinuously with the above modification to the 3D printer.

FIG. 2 shows various such vertical bars printed from the composition ofExample 1.

FIGS. 3 and 4 show photographs of various complex objects that can beprinted from the composition of Example 1.

Example 2

In a glass bottle, Ru-1 (1 molar part), CPTX (8 molar parts), Irganox1076 (1 phr), Irgafos 168 (0.25 phr) and BTBBT (0.7 molar parts) weredissolved in HexylTD (9,000 molar parts) and CPD3 (1,000 molar parts) toform a clear solution. The solution was purged with nitrogen for 8hours. UV DSC (measures at 30° C. after 4 sec of 400 nm UV lightexposure) was used to monitor the heat of reaction at different exposureintensities and the results are summarized in Table 1. This compositionwas also used in Hunter Flashforge 3D DLP printer. The viscosity of thecomposition remained same even after 12 hours of continuous printingwith one hundred percent light intensity and 25 seconds exposure timeper layer.

TABLE 1 120 mW/cm² 250 mW/cm² 750 mW/cm² Heat of Reaction 142 J/g 314J/g 445 J/g

Examples 3-5

In a glass brown bottle, CPTX (0.25 phr), Irganox 1076 (1 phr), Irgafos168 (0.25 phr), DMAP (0.2 molar part), and BTBBT (0.01 phr) weredissolved in HexylTD (10,000 molar parts) via sonication at 40° C. for 1hour to form a clear solution for the composition of Example 3. n-Butylacrylate was additionally added to this composition in appropriatequantities as listed in Table 2 for Examples 4 and 5. The solutions soformed in each of Examples 3 to 5 were purged with nitrogen for 8 hours.Ru-1 catalyst (1 molar part) was added in a glove box to each of thepurged solution and sonicated for 30 minutes to completely dissolve thecatalyst. Flashforge Hunter DLP 3D printer was used to conduct one-timeexposure of an image for 300 sec at 8 mW/cm² intensity. The imagesformed in each of Examples 3 to 5 consisted of lines and spacings ofvarious width. The composition kept in the vat of the printer wasblanketed with nitrogen.

TABLE 2 Example No. Butyl acrylate (molar parts) Example 3 0 Example 4 1Example 5 10

FIGS. 5 to 7 show photographs of the fabricated objects using thecomposition of Examples 3 to 5, respectively. It is quite apparent thatthe photographs of the objects formed from the compositions of Examples4 and 5 featured more clear lines, i.e., FIG. 6 and FIG. 7,respectively. This may perhaps be due to the fact that n-butyl acrylateaffectively minimized the dark reaction by trapping chloride radicalsthat were generated outside of the exposed area due to light scattering.

Comparative Example 1 Printing of 3D Objects without Nitrogen Blanket

The procedures of Example 1 were substantially repeated in thisComparative Example 1 except that no nitrogen blanket was used. FIG. 8shows a vertical bar made under these conditions. It is evident fromthis photograph that a significant non-uniformity of the printed partswas observed perhaps due to the presence of oxygen in the atmosphere.Also, it is evident that high oxygen level in the composition may haveinhibited the initiation of the polymerization reaction, and creatingvoids in the vertical bar. Attempts to print parts continuously from thesame vat did not result in forming any parts.

Comparative Examples 2-4

The procedures of Example 2 were substantially repeated in theseComparative Examples 2-4 except that no BTBBT was used in ComparativeExample 2, no BTBBT, Irganox 1076 and Irgafos 168 were used inComparative Example 3 and no Irganox 1076 and Irgafos 168 were used inComparative Example 4. UV DSC (measured at 30° C. after 4 sec of 400 nmUV light exposure) was used to monitor the heat of reaction at differentexposure intensities and the results are summarized in Table 3.

TABLE 3 120 mW/cm² 250 mW/cm² 750 mW/cm² 3D printing Comp. Ex. 2 222 J/g326 J/g 447 J/g no gelation Comp. Ex. 3 311 J/g 333 J/g 443 J/g gelledComp. Ex. 4 294 J/g 375 J/g 450 J/g partially gelled

It is evident from the results presented in Table 3 that the compositionof this invention exhibits surprisingly superior properties whenprocessed in accordance with the process of this invention. That is, acomposition containing the UV blocker in accordance with the compositionof this invention exhibits superior properties only when processedproperly under nitrogen atmosphere.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A composition comprising: a) one or more monomersof formula (I):

wherein: m is an integer 0, 1 or 2; R₁, R₂, R₃ and R₄ are the same ordifferent and each independently selected from the group consisting ofhydrogen, halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,perfluoro(C₁-C₁₂)alkyl, hydroxy(C₁-C₁₆)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl, tri(C₁-C₆)alkoxysilyl and a group offormula (A):—Z-Aryl  (A) wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,(CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₃-C₆)alkyl,hydroxy, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; Aryl is phenyl or phenylsubstituted with one or more of groups selected from the groupconsisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl, hydroxy,methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; b) an organo-ruthenium compoundselected from the group consisting of a compound of formula (II) and acompound of formula (III):

wherein L is P(R)₃, wherein each R is independently selected from thegroup consisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl,(C₃-C₈)cycloalkyl and (C₆-C₁₀)aryl; R₇ and R₈ are the same or differentand each independently selected from the group consisting of methyl,ethyl, linear or branched (C₃-C₆)alkyl, methoxy, ethoxy and linear orbranched (C₃-C₆)alkyloxy; R₉ is selected from the group consisting ofmethyl, ethyl, linear or branched (C₃-C₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl; Ar₁, Ar₂ and Ar₃ are the same or different andeach independently selected from the group consisting of substituted orunsubstituted phenyl, substituted or unsubstituted biphenyl andsubstituted or unsubstituted naphthyl, wherein each of said substituentsare independently selected from the group consisting of methyl, ethyland linear or branched (C₃-C₆)alkyl; c) a compound of formula (IV) or acompound of formula (V):

wherein n is an integer from 0 to 4; each R₁₀ is independently selectedfrom the group consisting of hydrogen, methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl and tert-butyl; R₁₁ is selected from thegroup consisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl,(C₆-C₁₀)aryl, methoxy, ethoxy, linear or branched (C₃-C₆)alkoxy,(C₆-C₁₀)aryloxy and halogen; d) a photoactive compound of formula (VI):

wherein Y is halogen; and R₃₀ and R₃₁ are the same or different andindependently of each other selected from the group consisting ofhydrogen, methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)aryloxy; and e) a compound offormula (VII):

wherein n is an integer from 0 to 4; each R₃₂ is independently selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)aryloxy;and said composition is in a clear liquid form at room temperature. 2.The composition according to claim 1, wherein said composition comprisesfirst and second monomer of formula (I) distinct from each other and oneof said first and second monomers having a refractive index of at least1.5 and viscosity below 100 centipoise, and wherein said first monomeris completely miscible with said second monomer to form a clearsolution.
 3. The composition according to claim 1, wherein the monomerof formula (I) is selected from the group consisting of:


4. The composition according to claim 1, wherein: L is selected from thegroup consisting of P(iPr)₃, P(tert-Bu)₃, PCy₃ and PPh₃; R₇ and R₈ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl, ethyl and isopropyl; R₉ is selected fromthe group consisting of hydrogen, methyl, ethyl and isopropyl; Ar₁, Ar₂and Ar₃ are the same or different and each independently selected fromthe group consisting of phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl,2,6-di(isopropyl)phenyl and 2,4,6-trimethylphenyl.
 5. The compositionaccording to claim 4, wherein the organo-ruthenium compound of formula(II) or organo-ruthenium compound of formula (III) is selected from thegroup consisting of:


6. The composition according to claim 1, wherein: n is an integer from 0to 2; each R₁₀ is independently selected from the group consisting ofmethyl, ethyl, iso-propyl and tert-butyl; and R₁₁ is selected from thegroup consisting of methyl, ethyl, iso-propyl, tert-butyl, phenyl,methoxy, ethoxy, phenoxy, fluorine and chlorine.
 7. The compositionaccording to claim 1, wherein the compound of formula (IV) is selectedfrom the group consisting of: N,N-dimethylpyridin-4-amine;N,N-diethylpyridin-4-amine; N,N-diisopropylpyridin-4-amine;N,N-di-tert-butylpyridin-4-amine; N,N-dimethyl-2-methylpyridin-4-amine;N,N-di-tert-butyl-2-methylpyridin-4-amine;2-methoxy-N,N-dimethylpyridin-4-amine;2-fluoro-N,N-dimethylpyridin-4-amine; N,N-dimethylquinolin-4-amine;N,N,2-trimethylquinolin-4-amine; 2-methoxy-N,N-dimethylquinolin-4-amine;and 2-chloro-N,N-dimethylquinolin-4-amine.
 8. The composition accordingto claim 1, wherein the compound of formula (VI) is selected from thegroup consisting of:


9. The composition according to claim 1, wherein the compound of formula(VII) is selected from the group consisting of:


10. The composition according to claim 1, which is selected from thegroup consisting of: a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1); a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1); a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1); a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-dimethylphenyl-imino)methyl)phenoxy)ruthenium(Ru-2); a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diethylphenyl-imino)methyl)phenoxy)ruthenium(Ru-3); a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-4); and a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-3-phenyl-1H-inden-1-ylidene)-2-(methylthio)phenoxy-ruthenium-triphenylphosphinechloride (Ru-5).
 11. A kit for forming a substantially transparent filmcomprising: a) one or more monomers of formula (I):

wherein: m is an integer 0, 1 or 2; R₁, R₂, R₃ and R₄ are the same ordifferent and each independently selected from the group consisting ofhydrogen, halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,perfluoro(C₁-C₁₂)alkyl, hydroxy(C₁-C₁₆)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, tri(C₁-C₆)alkoxysilyl and a group offormula (A):—Z-Aryl  (A) wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,(CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₃-C₆)alkyl,hydroxy, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; Aryl is phenyl or phenylsubstituted with one or more of groups selected from the groupconsisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl, hydroxy,methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; b) an organo-ruthenium compoundselected from the group consisting of a compound of formula (II) and acompound of formula (III):

wherein L is PR₃, wherein each R is independently selected from thegroup consisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl,(C₃-C₈)cycloalkyl and (C₆-C₁₀)aryl; R₇ and R₈ are the same or differentand each independently selected from the group consisting of methyl,ethyl, linear or branched (C₃-C₆)alkyl, methoxy, ethoxy and linear orbranched (C₃-C₆)alkyloxy; R₉ is selected from the group consisting ofmethyl, ethyl, linear or branched (C₃-C₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl; Ar₁, Ar₂ and Ar₃ are the same or different andeach independently selected from the group consisting of substituted orunsubstituted phenyl, substituted or unsubstituted biphenyl andsubstituted or unsubstituted naphthyl, wherein each of said substituentsare independently selected from the group consisting of methyl, ethyland linear or branched (C₃-C₆)alkyl; and c) a compound of formula (IV)or a compound of formula (V):

wherein n is an integer from 0 to 4; each R₁₀ is independently selectedfrom the group consisting of methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl and tert-butyl; R₁₁ is selected from the groupconsisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl,(C₆-C₁₀)aryl, methoxy, ethoxy, linear or branched (C₃-C₆)alkoxy,(C₆-C₁₀)aryloxy and halogen; d) a photoactive compound of formula (VI):

wherein Y is halogen; and R₃₀ and R₃₁ are the same or different andindependently of each other selected from the group consisting ofhydrogen, methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)aryloxy; and e) a compound offormula (VII):

wherein n is an integer from 0 to 4; each R₃₂ is independently selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)aryloxy.12. The kit according to claim 11, wherein the monomer of formula (I) isselected from the group consisting of:


13. The kit according to claim 11, wherein the organo-ruthenium compoundof formula (II) or organo-ruthenium compound of formula (III) isselected from the group consisting of:


14. The kit according to claim 11, wherein the compound of formula (IV)is selected from the group consisting of: N,N-dimethylpyridin-4-amine;N,N-diethylpyridin-4-amine; N,N-diisopropylpyridin-4-amine;N,N-di-tert-butylpyridin-4-amine; N,N-dimethyl-2-methylpyridin-4-amine;N,N-di-tert-butyl-2-methylpyridin-4-amine;2-methoxy-N,N-dimethylpyridin-4-amine;2-fluoro-N,N-dimethylpyridin-4-amine; N,N-dimethylquinolin-4-amine;N,N,2-trimethylquinolin-4-amine; 2-methoxy-N,N-dimethylquinolin-4-amine;and 2-chloro-N,N-dimethylquinolin-4-amine.
 15. The kit according toclaim 11, wherein the compound of formula (VI) is selected from thegroup consisting of:


16. The kit according to claim 11, wherein the compound of formula (VII)is selected from the group consisting of:


17. The kit according to claim 11, which contains a mixture selectedfrom the group consisting of: a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1); a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1); a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-1); a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-dimethylphenyl-imino)methyl)phenoxy)ruthenium(Ru-2); a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diethylphenyl-imino)methyl)phenoxy)ruthenium(Ru-3); a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium(Ru-4); and a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX),N,N-dimethylpyridin-4-amine (DMAP),(2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-3-phenyl-1H-inden-1-ylidene)-2-(methylthio)phenoxy-ruthenium-triphenylphosphinechloride (Ru-5).
 18. A film comprising the composition of claim
 1. 19. Afilm formed from the kit of claim
 11. 20. A process for forming a threedimensional printed article comprising: providing a compositionaccording to claim 1 in a container blanketed with an inert atmosphere;exposing to suitable UV radiation while drawing the composition from thecontainer; and forming the three dimensional article.